Dis azo imide containing dyestuffs



United States Patent 3,502,643 DIS AZO IMIDE CONTAINING DYESTUFFS Walter Horstmann, Cologne-Buchheim, Germany, and

Edgar Siege], Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Oct. 24, 1966, Ser. No. 588,708 Claims priority, application Germany, Nov. 2, 1965,

Int. c1. (:69!) 31/10 Suitable substituents X are, for example: lower alkyl substituents, such as methyl, chloro or nitro substituents; lower alkoxy substituents, such as -OCH or OC H fluoro, methyl-sulphonyl, trifluoromethyl and carbethoxy substituents.

Examples of radicalsA are:

1,4-phenylene; 4,4-diphenylene; 2,2'-dichloro-4,4'-diphenylene;

- 3 3'-dichloro-4 4-di hen l US. Cl. 260-452 8 Claims P y 3,3'-d1methyl-4,4'-diphenylene; 3,3'-dimethoxy-4,4'-diphenylene; and

ABSTRACT OF THE DISCLOSURE 1,2-ethy1ene radlcals- Azo dyestuffs which correspond to the formula: A Pmfeffed group of dyestuffs in the range 0f the products of the general Formula I corresponds to the formula s R-HNOO\ /CO-NI-IR I I /CHN=N 0| N=N-HC\ 0 H3000 b/K 000113 n ooc I H N-A- l A 00m A; l )m A 2 (la) in which R stands for hydrogen, or for methyl, chloronitro or methoxy substituents, R for hydrogen, or for methyl, chloro or nitro substituents, R for hydrogen or in which R stands for identicalor different radicals for chloro substituents, and A for an aliphatic, araliphatic, selected hrorn the group consisting of aromatic and aromatic or heterocyclic radical; the dyestuffs are free heterocyclic radicals, the radicals X stand for identical from sulphonic acid groups.

or different substituents, m stands for integers from The new azo dyestuffs are obtained, when azo com- 0 to 3, and A represents a member taken from the class pounds f the formula consisting of aliphatic, aromatic, and heterocyclic radicals.

The dyestuffs are free from sulphonic acid groups and 0 may be used as pigment dyestuffs for the coloring of CH 'N N plastics, lacquers, pigment pastes, and printing inks. 4O H300 O I e The object of the present invention is to provide valu- C able new azo dyestuffs which are free from sulphonic acid ).a H

groups and correspond to the general formula 0 (H) CHN=N 0 0 N=NHC II II H3000 x\/ COCH3 l 1 X m X In g (I) in which R denotes identical or different optionally subin which R, X and m have the same meaning as above,

stituted aromatic or heterocyclic radicals, the radicals X or functional derivatives of these azo-dicarboxylic acids,

are identical or different substituents, m stands for integers especially the monoor diesters, monoor diamides, from 0 to 3, and A is an aliphatic, araliphatic, aromatic dicarbonimides or anhydrides, are reacted with diamines or heterocyclic radical; by definition, the dyestulfs are of the general formula free from sulphonic acid groups.

The radicals R may be monoor polynuclear; radicals H2N A' NH2 (III) of the benzene and naphthalene series are preferred. in which A has the same meaning as above, in a molar Examples are the following radicals: phenyl; 2- or 3- or 4- ratio of components (II) to component (III) of approximethylphenyl-l; 2- or 3- or 4-chlorophenyl-1 2- or 3- or 4- mately 2: 1, in the presence of acidic condensation agents,

methoxyphenyl-l; 2-methyl-4-chlorophenyl-l; 2,4-dimeththe components being so chosen that the final dyestuffs ylphenyl-l; 3-nitro-phenyl-l and 2,5-dimethoxy-4-chlorophenyl-l radicals.

are free from sulphonic acid groups.

The reaction of the starting components is preferably carried out in a high-boiling organic solvent or solvent mixture, and the components themselves may also serve as organic solvents. The condensation takes place at an elevated temperature, generally in the range of 80240 C., preferably between 130 C. and 180 C.

The monoazo compounds of the general Formula II are prepared in the usual manner by diazotising the optionally substituted 3-amino-phthalic acids or their functional derivatives, and coupling with suitable acetoacetic acid amides, the components being free from sulphonic acid groups. Diazo components which can be used for the preparation of the azo compounds (II) are, for example:

3-amino-phthalic acid; 3-amino-phthalic acid monoand diesters, such as 3-amino-phthalic acid monomethyl ester-(l) or 3- amino-phthalic acid dimethyl ester; 3-a-mino-phthalimide; 3-amino-6-methyl-phthalic acid; 3-amino-5-nitro-phthalic acid; 3-amino-6-nitro-phthalic acid; 3-amino-6-methoxy-phthalic acid; 3-amino-6-chloro-phthalic acid; 3-amino-4-methoxy-phthalic acid; 3-amino-6-bromo-phthalic acid; 3-amino-6fluoro-phthalic acid; 3-amino-5,6-dimethoXy-phthalic acid; 3-amino-4,5,G-trimethoxy-phthalic acid; 3-amino-5,6-methylene-dioxide-phthalic acid; 3-amino-5-eyano-phthalic acid; 3-amino-6-cyano-phthalic acid; 3-arnino--5-methoxy-6-ethoxy-phthalic acid; 3-amino-6-methylsulphonyl-phthalic acid; 3-amino-4-methyl-phthalic acid; 3-amino-5-carbethoxy-phthalic acid; 3-amino-6-carbethoxy-phthalic acid.

Coupling components which can be used for synthetising the monoazo compounds (II) are, for example:

acetoacetic acid anilide;

acetoacetic acid-2-chloro-anilide; acetoacetic acid-2,4-dimethyl-anilide; acetoacetic acid-Z-methyl-anilide; acetoacetic acid-2,5-dimethoxy-4-chloro-anilide; acetoacetic acid-Z-methoxy-anilide; acetoacetic acid naphthyl-(1)-amide; acetoacetic acid-2-methyl-3-chloro-anilide; acetoacetic acid-4-methyl-anilide; acetoacetic acid-2-methyl-4-chloro-anilide; acetoacetic acid-2,S-dichloro-anilide; acetoacetic acid-2,4-dichloro-ani1ide; acetoacetic acid-Z-nitro-4-chloro-ani1ide; acetoacetic acid-Z-nitro-4-methyl-anilide; acetoacetic acid-Z-nitro-anilide; acetoacetic acid-2-nitro-4-methoxy-anilide; acetoacetic acid-2-methoXy-4-nitro-anilide; acetoacetic acid-2-chloro-4-nitro-anilide; acetoacetic acid-2,4-dinitro-anilide; acetoacetic acid-4-nitro-anilide; acetoacetic acid naphthyl-(2)-amide; acetoacetic acid-2,4,S-trichloro-anilide; acetoacetic acid-Z-methyl-S-nitro-anilide; acetoacetic acid-2-methoxy-5-nitro-anilide; acetoacetic acid-3-nitro-ani1ide; acetoacetic acid pentachloro-anilide; acetoacetic acid-2-methyl-4-nitro-anilide; acetoacetic acid-2-methyl-S-nitro-anilide; acetoacetic acid-Z-methyl-S-chloro-anilide; acetoacetic acid-3-chloro-anilide; acetoacetic acid-4-ethoxy-anilide; acetoacetic acid-2,4xlimethyl-5-chloro-anilide; acetoacetic acid-2-(6-ethoxy-benzothiazolyl)-amide; acetoacetic acid-2-(benzotl1iazoly1)-amidc.

The corresponding alkyl, aryl or aralykyl monoand diesters and the anhydrides or imides of the above substituted phthalic acids can also be used with advantage. The esters have the advantage of being readily soluble in a high-boiling organic solvent used for the condensation.

The following aliphatic, araliphatic, aromatic and heterocyclic diamines, for example, are used for the condensation of the monoazo compounds (II) with the diamines (III) which is carried out according to the invention in high-boiling organic solvents with the addition of acidic condensation agents:

1,2-ethylene-diamine;

4,4'-diamino-diphenyl; 2,2-dichloro-4,4'-diamino-diphenyl;

3 ,3 -dichloro-4,4-diamino-diphenyl; 2-nitro-4,4'-diamino-diphenyl;

3 ,3 '-dimethoXy-4,4'-diamino-diphenyl;

3 ,3 -diethoxy-4,4-diamino-diphenyl;

3 -methyl-4,4-diamino-diphenyl;

3 ,3 -dimethyl-4,4'-diarnino-dipheny1;

3 ,3 -dimethyl-4,4-diamino-6,6-dinitro-diphenyl; 2,2'-dimethy1-4,4'-diamino-diphenyl; 2,2'-dichloro-4,4'-diamino-S ,5 '-dimethoXy-diphenyl; 2,2,5 ,5 -tetrachloro-4,4'-diamino-diphenyl;

3 ,3 ,5 ,5 '-tetrach1oro-4,4'-diamino-diphenyl;

3 ,3 ,5 ,5 '-tetramethyl-4,4'-diamino-diphenyl; perchloro-4,4-diamino-diphenyl; l,4-diamino-benzene;

1,3-diamino-benzene; 2-chloro-1,4-diamino-benzene;

2,5 -dichloro -1,4-diamino-benzene; 2,6-dichloro-1,4-diamino-benzene; 2-nitro-1,4-diamino-benzene;

2,5 -diethoxy- 1 ,4-diamino-benzene; Z-methyl-S-methoxy-1,4-diamino-benzene; tetrachloro-p-phenylene-diamine; tetrachloro-m-phenylene-diamine; 4,4-diamino-diphenyl ether; 4,4-diamino-diphenyl-sulphone;

3 ,3 -diamino-4,4'-dichloro-diphenyl-sulphone; 3 ,3 '-diamino-4,4'-dimethoxy-diphenyl-sulphone; 4,4'-diamino-diphenylketone;

3,3 -diamino-diphenylketone;

3 ,3 '-diamino-4,4-dichloro-diphenylketone; 3,3 -diamino-4,4-dimethoxy-diphenylketone; 4,4-diamino-diphenylmethane;

3 ,3 '-diamino-diphenylmethane; 4,4-diamino-3 ,3 ,5 ,5 '-tetrachloro'diphenylmethane; 4,4'-diamino-stilbene; 4,4'-diamino-benzanilide; 4,4-diamino-diphenyl-ethane (sym.); 4,4'-diamino-azobenzene; 2,8-diamino-chrysene; 1,4-diamino-napthalene;

1,5 -diamino-naphthalene; 2,6-diamino-naphthalene; 2,7-diamino-naphthalene;

2- 4'-amino-phenyl -5-amino-benzotriazole; 2,5- (4,4-diamino-phenyl) -oxdiazole; 4,4'-diamino-diphenyl-urea;

3 ,3 -dimethoxy-4,4'-diamino-stilbene; 2,6-diamino-benzothiazole;

2- 4'-amino-phenyl -6-amino-benzothiazole; 2,7-diamino-fluorene;

2,7 -diamino-diphenylene-oxide; 2,7-diamino-diphenylene-sulphone;

2,5 (4,4-diamino-phenyl -thiadiazole;

2,5 (4,4-diamino-phenyl) -triazole.

The following solvents boiling above C. may be mentioned, by way of examples, for the condensation of the monoazo compounds (II) with the diamines (III) in high-boiling organic solvents: glacial acetic acid, toluene, xylenes, chlorobenzene, 0-, m-, p-dichlorobenzene,

1,2,3-, 1,2,4- and 1,2,5-trichlorobenzene, nitrobenzene, quinoline and mixture of such solvents.

Suitable condensation agents are, for example: acetic acid, propionic acid, mono-, diand trichloro-acetic acid, hydrochloric acid, sulphuric acid, ortho-phosphoric acid, aluminium chloride, ferric chloride, zinc chloride and anhydrous sodium acetate.

The reaction of the dicarboxy-azo compounds (II) or their functional derivatives with the diamino components (III) is carried out in a ratio of approximately 2:1. A slight excess of the components (II) is frequently desirable in order to react the component (III) completely.

Symmetrical or asymmetrical dyestuffs of the formula (I) can be synthetised, dependent upon the choice of the components (II). To produce the preferred group of dyestuifs of the Formula Ia, a diamine of the Formula III is condensed with an azo-dicarboxylic acid of the formula temperature and are preferably used for colouring plastics, for example polyvinylchloride, acrylonitrile-styrenebutadiene-copolymerisates and -graft-copolymerisates, lacquers or papers, and for producing printing inks and pigment pastes.

Belgian patent specification No. 652,251 already mentions pigment dyestuffs of the general formula in which K is defined as the radical of any coupling component, A as an aromatic or heterocyclic system and R as a bivalent alkyl, aryl, aralkyl or hetero radical.

However, this patent specification does not contain a single example of a dyestulf of the general formula stated therein and not even an example for only one of the components K, A or R The patent specification otherwise contains only a few, very general statements regarding processes for the production of the pigment dyestuifs.

The following examples are given for the purpose of illustrating the invention; the parts are parts by weight and the temperatures are given in degrees centigrade.

EXAMPLE 1 47.7 parts 3-amino-phthalic acid are suspended in 500 parts water, 83 parts concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 18.3 parts sodium nitrite in 50 parts water. The excess nitrite is removed by means of amidosulphonic acid.

The diazo suspension is added portionwise at 5l0 to a solution of 56 parts acetoacetic acid-2-chloroanilide in 250 parts ethanol, which has been mixed with a solution of 45 parts caustic soda in 80 parts water. When the coupling is completed, the reaction mixture is acidified (pH 1-2), the yellow dystuif is filtered oif with suction, washed with Water until free from acid and dried in a drying cabinet at 6080. There are thus obtained 90 parts mono- Cl HOOC COOH For conversion into the corresponding anhydride, the dry powdered monoazo-o-dicarboxylic acid is suspended in 500 parts chlorobenzene, 50 parts acetic anhydride are added and the mixture is heated at about 120 for 3-4 hours. The anhydride which is precipitated in crystalline form is filtered off with suction at room temperature, washed With light petrol and dried at in a drying cabinet. From parts dicarboxylic acid there are obtained 68 parts anhydride, M.P. 275277.

8.50 parts of the monoaZo-o-dicarboxylic anhydride and 1.08 parts phenylene-diamino-1,4 are suspended in 550 parts o-dichlorobenzene, 50 parts glacial acetic acid are added and the mixture is slowly heated to 140.

During heating, a clear solution first results, then, after about one hour, the hardly soluble pigment begins to separate. The mixture is heated for about 25 hours, then cooled to 40-60", the product is filtered off with suction, washed with parts chlorobenzene at 70-80, and subsequently with light petrol, and dried at 80 in a drying cabinet. The yield is 7.5 parts of the greenish yellow pigment of the formula The pigment so obtained has a very good fastness to lacquer coating at and 170. The fastness to light is also very good.

EXAMPLE 2 38.3 parts 3-amino-phthalic acid are suspended in 400 parts water, 72 parts concentrated hydrochloric acid are added and the mixture is diazotised at -05 with a solution of 14.7 parts sodium nitrite in 50 parts water. The excess nitrite is removed by means of amidosulphonic acid.

The resultant diazo suspension is added portionwise to a solution of 48 parts acetoacetic acid-2-methyl-4-chloroanilide in 200 parts ethanol, which has been mixed with a solution of 34 parts caustic soda in 65 parts water, so that the temperature remains between 5 and 10. As soon as the coupling is completed, the mixture is adjusted to pH 1-2 by the addition of 1 0% hydrochloric acid, the dyestuif is filtered off with suction, washed with water until free from acid, and dried in a drying cabinet at 80. The yield is 85 parts dyestutf-o-dicarboxylic acid.

The dicarboxylic anhydride of the dyestulf is obtained by heating with 50 parts acetic anhydride in 500 parts chlorobenzene at 110420 for 3-4 hours, M.P. 315.

90 parts of the dyestulf-o-dicarboxylic acid or 8.5 parts of the anhydride are suspended in 500 parts o-dichlorobenzene, 1.84 parts 4,4'-diamino-diphenyl and 50 parts glacial acetic acid are added and the mixture is heated to The starting components are thereby first completely dissolved. After about 30 minutes a hardly soluble product begins to separate. The mixture is kept at 140 for 25 hours in all, then cooled to 60, the product is filtered oif with suction, washed with 300 parts chlorobenzene at 70-80 and then with light petrol, and dried at 80 in a drying cabinet. This method yields 8.7 parts of a greenish yellow pigment dyestuif of very good fastness to light and lacquer coating.

7 EXAMPLE 3 47.7 parts 3-amino-phthalic acid are suspended in 5 parts water, 83 parts concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 18.3 parts sodium nitrite in 50 parts Water. The excess nitn'te is removed by means of amidosulphonic acid.

A solution of 45 parts caustic soda in 80 parts water is added to a suspension of 51 parts acetoacetic acid-2 methylanilide in 250 parts ethanol, the mixture is cooled to -10 and the above diazo suspension is added in portions. As soon as the coupling is completed, the mixture is acidified with hydrochloric acid (1:1, pH 1-2), the prodnot is filtered OE With suction, Washed with water until free from acid and dried in a drying cabinet at 80. The yield of monoazo-o-dicarboxylic acid is 91 parts.

By heating with 500 parts chlorobenzene and 50 parts acetic anhydride at 110-120 for 3-4 hours, cooling to filtering off with suction, washing the residue with light petrol and drying, there are obtained 66 parts monoazo-o-dicarboxylic acid anhydride, M.P. 273-2763 8.5 parts monoazo-o-dicarboxylie acid or 8.0 parts of the anhydride are suspended in 500 parts o-dichlorobenzene and parts glacial acetic acid, 0.6 part ethylenediamine is added and the mixture is then heated at 140 for 25 hours.

The mixture is subsequently cooled to the precipitated yellow pigment is filtered off with suction, washed with 120 parts chlorobenzene at and then with light etrol, and then dried in a drying cabinet at 80.

Yield: 6.9 parts of pigment with very good fastness properties.

Valuable yellow to brown pigment dyestuffs are also obtained, when the procedures described in these examples are followed, but, instead of the diaZo components, coupling components and diamines there specified, there are used the diazo and coupling components and the diamines listed in the following Table, the dyestuffs from 3-amino-phthalic acid and the stated coupling components being employed in the form of the free dicarboxylic acid or of the anhydride.

Diazo component Coupling component Diamine 3-arnino-p'nthalic acid- Acetoacetic acid-2 chloro-anilide Ethylene-diamine.

Do do 4,4-diemino-diphenyl.

do Acetoaeetic acid-naphthyl-(2)-amide Ethylele-diamine.

do L Acetoacetie acid-2-methyl-3-chlord anilid 1,3-diamino-benzene.

2,2-dichloro-4,4-diamino-dipheuyl. 3,3-dichloro 4,4-diamino-diphenyl. 3,3-dimetl1yl-4,4-diernino-diphenyl. 3,3-dimethoxy-4,4-diaminodipheuyl. 4,4-diamiuo-benzophenone.

1,4-diaminobenzene. 1,3-diamino-benzene. 4.4-diamino-diphenyl. 2,2-diehloro-l 4-diamiu0-diphenyl. 3,3-dichloro-4,4=diamino-dipheny]. 3.3-din1ethy1-4,4-diamino-diphenyl. 3,3dimethoxy-4,4-diamino-diphenyl. 4,4-diamino-benzophenone. 4,4-diamino-stilbene. 3,3-dimethoxy-4,4-diamino-stilbene. 2,7-diamino diphcnylene oxide.

Ethylene diamine.

L-phenylene diamine. 2,2-dichlorol,4-diaminodiphenyl. 3,3-dichloro-4,4-diamino-dipheny]. 3,3-dimethyl-4,4-diamino-diphenyl. 3,3-dimethoxy-4,4-diamino-diphcnyl. 2,7-diamino-tiuorene.

2,7-diamino diphenylene-sulphone. 2,5(4,4-diamino-phenyl)-oxdiazole. 2,5-(4,4-diamino-phenyl)-th1adiazole. Ethylene-diamine. 1,4-phenylene-diarnine. 4,4'-diarnino-dipheny1.

2,2dichloro 4,4-diamino-diphenyl. 3,3-dichloro-4,4-diamino-di henyl. 3,3-dimethyl-4,4'-diaminoiphenyl. 3,3-dimeth0xy-4,4'dieminodiphenyl. 2,6-diamino-naphthalene. 1,5-diamino-naphthalene. 4,4diarnino-diphenyl ether. Ethylenediamine. 1,4-phenylene-diarnine. 4,4-diamino-diphenyl. 3,3-dimethyl-4,4-tliamino-diphenyl. 3,3-dichloro-4,4-diamino-diphenyl. 3,3-dimethoxy-4,4-diamino-diphenyl. Ethylene-diamine.

lA-phenylene-diamine. 4,4-diamino'diphenyl. 3,3-dimethyl-4,4-diamino-diphenyl, 3,3 dichl01'0-4,4-diamino-diphenyl. 3,3-dimethoxy-4,4-diaminc-diphenyl. Ethylene-diamine. 1,4-phenylenediamine. 4,4"-diamino-stilbene. 4,4-diamino-benzanilide. 3,3-dimethyl-4,4-diamino-diphenyi.

lA-phcnylene-diamine.

3,3- dimethyl-4,4-diamino-diphanyl. 1,4-diamino-benzene. 4,4-diamine-diphenyl-methane. 4,4diamino-diphenyl.

2,2-dichloro-4,4-diamino-diphenyl.

Ethylene-diamines.

Do Aeetoac etic acid-fiiiiii'e'tiidi i- 4,4-diamino-diphenyl.

chloro-anilide.

3,3-dirnethyl-4,4-diamino-diphenyl.

3,3-diehloro-4,4-diamino-diphenyl.

........ 2,2-dichloro-4,4'-diamino-diphenyl.

4,4-diamino-benzophenone.

l,4-diaminobenzene.

4,4-diamino diphenyl. 8,3-dlmathyl4,4dlamino dlghenyl.

Diazo component Coupling component Diamlne 3-amilno-4-chlorophthalic Acetoacetic acid-anilide 1,4-diam.lno-benzene.

aci

Do do Ethylene-diamine. Do Acetgagetic acid-2-methyl-4-chloro- 1,4-diamino-benzene.

am 1 e. D do 4,4'-diarnino-diphenyl. Do. Acetoacetic acid-2,5dimethoxy4- Ethylenediamine.

chloro-anilide D0 do 1,4-diamino-benzene. Do do. 4,4-diaminodiphenyl. 3amino-4,5-dichloro- Acetoacetic acid-anilide. 1,4-diamino-benzene. phthalic acid.

D0 do 4,4-diamino-diphenyl.

do Ethylene-diamine'. Do Aceti afetic-2,5dimethoxy-4-chloro- 1,4-diamin0-benzene.

am 1 e. ..do... 4,4'-diamino-diphenyl. Do ..-do Ethylene-dlamine. D0 Acetoliagetie aeid-2,4-dimethyl- 1,4-diamino-benzene.

an] 6. Do. do 4,4diamino-diphenyl. Do do Ethylene -diamine. 3-ammo-6-methoxy- Acetoacetlc acid-anilide 1,4-diamindbenzene.

phthalic acid.

Do do Ethylene-diamine. D0 Acetoaeetic acid2,5-dirnethoxy4 1,4-diamino-benzene. chloroanilide.

.... do. 4,4-diamino-diphenyl-methane.

Ethylene-diamine;

1,44%amino-benzene. o. Acetoaeetic acid-Z-methoxy-anilide Do. Do Acetoacetic acld-2-methyl-4-ehloro- Do.

anilide. Do Acetoaeetio acid-2,4-dimethyl- Do.

anilide.

EXAMPLE 4 EXAMPLE 6 9.7 parts of the anhydride of the formula 9.8 parts of the azodyestufi of the formula Cl 0 OH; I

Cl NHC OCHN:N o1- NHC O-CH-N=N a (g C 0 O 0 H3 0 CH Cl- C O O H on. 1

COOH C0 are heated for 1 hour at 130 C. in a mixture of 300 parts and 1.08 parts of 1.4-diamino-benzene are suspended in a mixture of 250 parts o-dichlorobenzene and 25 parts glacial acetic acid. The mixture is heated for 5 hours at 130135 C., then cooled to 60 C., the product is filtered off with suction, washed with chlorobenzene at 60 C. and subsequently dried at 80 C. in a drying cabinet. The yield is 9.15 parts of a yellow pigment of the formula 3 mooc I The pigment so obtained has an excellent fastness to migration in polyvinylchloride and fastness to heat up to temperatures of'about 280 C. The pigment is very useful for the dyeing of acrylonitrile-etyrene-butadiene-copolymerisates and graft-copolymerisates.

EXAMPLE 5 9.7 parts of the anhydride of Example 4 and 0.6 part ethylene diamine are reflexed for 6 hours in a mixture of 500 parts o-dichloro-benzene and 50 parts glacial acetic acid. After cooling to 50-60 C. the precipitated pigment is filtered off with suction, washed with chlorobenzene and then dried in a drying cabinet at 80 C. Yield: 7.8 parts of pigment with very good fastness to light and heat.

o-dichlorobenzene and 30 parts glacial acetic acid. 2.27 parts 4,4'-diaminobenzanilide are added and heating is continued for 5 hours. The precipitated pigment is filtered off with suction at 60 C. and washed with o-dichlorobenzene at 60 C. and subsequently dried at 80 C. in a drying cabinet. Yield: 10.1 parts of a yellow pigment with very good fastness properties.

EXAMPLE 7 8.0 parts of the anhydride of the formula OCH;

and 1.08 parts of 1,4-diamino-benzene are heated for 10 hours at 120 C. in a mixture of 200 parts p-xylene and 20 parts glacial acetic acid. The precipitated pigment is filtered oil with suction at C., washed with p-xylene at 60 C. and dried in a vacuum oven at 60 C. The yield is 7 .8 parts of the pigment of the formula 11 What is claimed is: 1. A20 dyestuffs which are free from sulphonic acid groups and which correspond to the formula:

in which R stands for identical or different radicals selected from the group consisting of phenyl, naphthyl, 2-benzothiazolyl, substituted phenyl, substituted naphthyl radicals, and substituted Z-benzothiazolyl, wherein the substituents are methyl, chloro, nitro, methoxy, or ethoxy; X stands for identical or different substituents selected from the group consisting of lower alkyl, lower alkoxy, nitro, halo, trifiuoromethyl, carbethoxy, methylsulphonyl, and cyano radicals; m is an integer from to 3; and A is selected from the group consisting of phenylene, diphenylene, phenylene-Ri -phenylene, substituted phenylene, substituted diphenylene, and substituted phenylene-R -phenylene wherein the substituents are selected from the group consisting of --Cl, -CH -OCH OC H and NO ethylene, naphthylene, and divalent radicals selected from the group consisting of and 12 and wherein R is selected from the group consisting of O-, SO

0 ll C CH CH=CH, -NHCO, NHCONH, and -N= 2. A20 dyestuffs which are free from sulphonic acid groups and which correspond to the formula:

in which R stands for a member taken from the class consisting of hydrogen, methyl, chloro, and methoxy groups; R stands for a member taken from the class consisting of hydrogen, methyl, chloro, and nitro groups; and R denotes radicals selected from the group consisting of hydrogen and chloro and wherein A represents a member taken from the class consisting of phenylene, diphenylene, phenylene-R -phenylene, substituted phenylene, substituted diphenylene, and substituted phenylene-R phenylene wherein the substituents are selected from the group consisting of -Cl, CH OCH --OC H and -NO ethylene naphthylene, and divalent radicals selected from the group consisting of and wherein R is selected from the group consisting of --O, SO

13 3. The dyestuff of the formula OCH 4. The dyestuff of the formula O CH CH3 3 NCH2- 5. The dyestufl of the formula 6. The dyestutf of the formula 14 7. The dyestuff of the formula OCH OO J References Cited FOREIGN PATENTS 12/1964 Belgium.

CHARLES B. PARKER, Primary Examiner DONALD M. PAPUGA, Assistant Examiner US. Cl. XR. v 84, 7, 41, 106-22, 288; 260-37, 157, 158, 193 

